WO2010128650A2 - Matière à base de carbone et son procédé de fabrication - Google Patents

Matière à base de carbone et son procédé de fabrication Download PDF

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WO2010128650A2
WO2010128650A2 PCT/JP2010/057725 JP2010057725W WO2010128650A2 WO 2010128650 A2 WO2010128650 A2 WO 2010128650A2 JP 2010057725 W JP2010057725 W JP 2010057725W WO 2010128650 A2 WO2010128650 A2 WO 2010128650A2
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graphite
carbon material
vapor
porous carbon
carbon
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PCT/JP2010/057725
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WO2010128650A3 (fr
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一生 村松
豊田　昌宏
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株式会社インキュベーション・アライアンス
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Priority to JP2011512349A priority Critical patent/JP5613662B2/ja
Priority to CN201080019171.9A priority patent/CN102414125B/zh
Priority to EP10772169.8A priority patent/EP2431326B1/fr
Priority to US13/266,295 priority patent/US8883112B2/en
Priority to ES10772169.8T priority patent/ES2606284T3/es
Priority to KR1020117026928A priority patent/KR101446638B1/ko
Publication of WO2010128650A2 publication Critical patent/WO2010128650A2/fr
Publication of WO2010128650A3 publication Critical patent/WO2010128650A3/fr
Priority to US14/504,033 priority patent/US9379385B2/en

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    • C04B35/62605—Treating the starting powders individually or as mixtures
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Definitions

  • the present invention relates to a carbon material that can be suitably used for battery materials such as lithium ion batteries, various capacitors, fuel cell electrodes, and various catalyst materials.
  • graphite materials are used for lithium ion battery negative electrodes and electric double layer capacitor negative electrodes because they are suitable for intercalation reaction with lithium ions and the like.
  • a compound in which an alkali metal such as lithium or potassium, an ion such as a sulfate ion or a nitrate ion is inserted between layers of the carbon lead hexagonal mesh surface (FIG. 1) by intercalation is called a graphite intercalation compound.
  • graphite materials are used as electrode materials because electrical energy is obtained by the generation of graphite intercalation compounds as described above, intercalation of intercalation inserted between layers, and deintercalation. in use.
  • Non-Patent Document 1 In the intercalation reaction between graphite material and intercalation (substance to be inserted), there is a correlation between the degree of graphitization (crystallinity) and reactivity of graphite, which is the host material. In the donor type in which intercalation occurs as ions, the reactivity with a host material having a high degree of graphitization is good. Examples of the intercalation that causes intercalation as a donor type include alkali metals such as lithium, sodium, potassium, and cesium, and alkaline earth metals such as barium and strontium. (Non-Patent Document 1)
  • donor-type graphite intercalation compounds are generally unstable in the air, react with oxygen and moisture, and the intercalant is discharged from the graphite layer (decalation).
  • the crystallite size is as large as several microns, and since it is not a complete single crystal, a part of the intercalant stays between the graphite layers to form a so-called residual compound.
  • the end of the carbon hexagonal mesh surface is located on the outer surface of the graphite material as the host material. No reaction occurs on parallel surfaces.
  • Naturally produced natural graphite quiche graphite that precipitates when the molten iron in the iron manufacturing process cools, graphite material that precipitates from the liquid phase under high temperature and high pressure conditions has high anisotropy and orientation, and the particle surface
  • the carbon hexagonal network surface itself is dominant, and the end of the carbon hexagonal network surface is limited to the end of the particle. (Fig. 7)
  • Resin such as polyacrylonitrile (PAN), carbon fiber made from coal and petroleum pitch are carbonized and graphitized by heat treatment that draws and pulls into fiber at the polymer material stage. For this reason, carbon fiber has a structure in which carbon hexagonal mesh faces are concentrically laminated in parallel to the fiber direction, or carbon hexagonal mesh faces are radially laminated.
  • the carbon hexagonal mesh surface is the dominant structure on the surface. Even in carbon fibers with a radial structure, it becomes a skin structure (a structure in which the radial structure lies on the surface) to maintain the fiber structure, and the carbon hexagonal mesh surface becomes the dominant structure. .
  • isotropic graphite material production method petroleum coke is used as an aggregate, petroleum and coal pitch are used as a binder, and preformed, carbonized, graphite using a cold isostatic press (CIP). There is a way to make it.
  • CIP cold isostatic press
  • isotropic graphite materials are isotropic as a material, the porosity of the material is less than 10% because a process of filling the filler with high density is essential, and it is difficult to provide strength.
  • Patent Document 5 The highly oriented graphite crystal disclosed in Japanese Patent No. 2633638 (Patent Document 5) grows vapor-phase-grown graphite in glassy carbon, but it is highly advanced until the bulk density is equivalent to 2.15. It is a filled high density graphite. For this reason, the ratio of the end portions of the graphite hexagonal mesh surface appearing on the outer surface is relatively low, and the porosity calculated from the difference between the bulk density and the true density is as low as several percent, resulting in poor reaction efficiency.
  • Conventional graphite materials basically have high anisotropy, and are composed of a surface in which the plane of the carbon hexagonal network surface is dominant and the edge of the material in which the edge of the carbon hexagonal network surface is dominant, increasing the heat treatment temperature. As the degree of graphitization increases, the anisotropy tends to increase. Intercalation reactions used in lithium ion batteries, capacitors, etc. occur at the end of the carbon hexagonal network surface, and the higher the degree of graphitization (crystallinity) as a graphite crystal, the higher the reaction efficiency, It has been difficult to produce a carbon material whose surface is composed of ends of carbon hexagonal mesh surfaces.
  • a polymer material that becomes carbon after heat treatment is formed into a predetermined shape, and carbonized and fired at a predetermined heating rate to produce a pre-fired body having appropriate closed pores therein.
  • the calcination temperature of carbonization calcination is set so that hydrocarbons and hydrogen, which are raw materials for vapor-grown graphite, can be appropriately generated in subsequent steps.
  • the carbon material containing hydrogen after carbonization and firing contains an appropriate concentration of hydrogen, and it is an essential condition that it appropriately contains closed pores that are the starting points for subsequent vapor-grown graphite formation.
  • Heat treatment of the above carbon material generates hydrocarbon gas such as methane and hydrogen gas from the material, and high-pressure pressurization by isotropic gas pressure so that these generated gas exists at high concentration around the material To do.
  • hydrocarbon gas such as methane and hydrogen gas
  • isotropic gas pressure so that these generated gas exists at high concentration around the material To do.
  • the amount of residual hydrogen after carbonization and firing and the closed porosity are set in appropriate ranges, the maximum temperature achieved during hot isostatic pressing after carbonization and firing is 1400 ° C. or higher, and the pressure is 10 MPa.
  • the crystallinity is high, and the carbon hexagonal network surface grows radially to produce a porous carbon material.
  • FIG. 2 and FIG. 3 show electron micrographs of the carbon material produced by the above method as substitute photos.
  • FIG. 3 is an enlarged photograph of FIG.
  • a porous carbon material is obtained in which the end of the carbon hexagonal mesh surface is located on the outer surface.
  • the thickness in the stacking direction of the carbon hexagonal network surface calculated from this electron micrograph was in the range of 0.01 to 0.2 microns.
  • FIG. 4 shows the Raman spectrum of the carbon material shown in FIGS.
  • a strong peak of 1580 cm ⁇ 1 due to the SP2 hybrid orbital of carbon is shown, and it has a highly crystalline graphite structure.
  • the value is a very low value of 0.085, and the structure is extremely excellent in graphite crystallinity.
  • a graphite intercalation compound using the carbon material produced by the above method as a host material was synthesized, and then rapidly heated to form a gap between carbon hexagonal networks. It is effective to be destroyed.
  • donor type binary systems such as alkali metals and alkaline earth metals
  • acceptor type binary systems such as sulfuric acid and nitric acid
  • organic ternary systems such as alkali metals and tetrahydrofuran, alkaline earth metals and tetrahydrofuran
  • alkalis Various graphite intercalation compounds such as metals, ethers, multi-component systems such as alkali metal earths and ethers can be suitably used.
  • the above-mentioned graphite intercalation compound is rapidly heated by throwing it into an electric furnace or the like maintained at a temperature of 600 ° C. or higher, thereby destroying the interlayer due to the graphite hexagonal mesh surface that is weakly bonded by van der Waals force. Produce vapor-grown graphite with a high rate.
  • the rapid heating temperature is raised to about 900 ° C. and the heating is performed more rapidly, the porous structure is destroyed and a graphite flake similar to graphene having a thickness of 0.001 to 0.01 microns can be obtained.
  • the porous structure is destroyed by applying physical impact such as application of impact at liquid nitrogen temperature, ultrasonic wave in a solvent, etc. to the obtained porous vapor-grown graphite structure, Graphene-like graphite flakes having a thickness of about 0.01 to 0.1 microns can be obtained.
  • Conventional graphite material has a large anisotropy, and the ratio of the end of the graphite hexagonal mesh surface located on the outer surface is low, but the ratio of the end of the graphite hexagonal mesh surface to the outer surface is extremely high, It becomes possible to produce a carbon material that is porous. As a result, an electrode material optimal for intercalation reaction and the like, and a carbon material for a catalyst material can be produced in large quantities at a low cost.
  • FIG. 3 is an enlarged photograph of FIG. 2 and a drawing-substituting photograph showing that the end of the carbon hexagonal mesh surface is located on the outer surface of the particle and is a porous material.
  • FIG. 4 It is a Raman spectrum figure of the vapor-phase growth graphite produced
  • Example 15 It is a scanning electron microscope (SEM) photograph of the graphite surface which is not porous but a dense form.
  • Example 16 It is a high-magnification SEM photograph of the graphite surface which is not porous but has a dense form.
  • Example 16 It is the schematic diagram which compared the structure of the conventional carbon material and graphite material, and the carbon material of this invention.
  • a polymer material that is carbonized with high yield after heat treatment is formed into a predetermined shape.
  • Specific examples of such polymer materials include petroleum pitch, coal pitch, asfeld, PVC pitch, tetrabenzophenazine pitch, naphthalene pitch, anthracene pitch, petroleum mesophase pitch, polyacrylonitrile, rayon, phenolic resin, A furan resin, a cellulose resin, or the like can be preferably used.
  • thermosetting resins Epoxy resins, novolak-type epoxy resins, polyfunctional epoxy resins, alicyclic epoxy resins, alkyd resins, urethane resins, and thermoplastic resins such as vinyl chloride resins, polyethylene, polypropylene Synthetic rubber such as polyisoprene and butadiene, synthetic rubber such as nylon, vinylon, acrylic fiber, rayon, etc.
  • polyvinyl acetate, ABS resin, AS resin, acrylic resin, polyacetal, polyimide, polycarbonate, modified Polyphenylene ether (PPE), polyethylene terephthalate, polybutylene terephthalate, polyarylate, polysulfone, polyphenylene sulfide, polyether ether ketone, fluororesin, polyamide imide, polyether ether ketone, silicon resin and the like can be used.
  • PPE Polyphenylene ether
  • polyethylene terephthalate polybutylene terephthalate
  • polyarylate polysulfone, polyphenylene sulfide, polyether ether ketone, fluororesin, polyamide imide, polyether ether ketone, silicon resin and the like
  • the polymer material can be formed into a desired shape (for example, a disk shape) by hot pressing or the like.
  • the molded polymer material is carbonized and fired at a predetermined temperature increase rate in an inert gas atmosphere such as nitrogen gas.
  • the heating rate is set so that many closed pores of several microns to several tens of microns are generated inside the material during carbonization firing.
  • the temperature range from room temperature to 500 ° C at a rate of temperature increase of 3 ° C or more per hour and the temperature range of 500 ° C or more at a rate of temperature increase of 5 ° C or more per hour, Carbonizes while producing closed pores of several microns to several tens of microns.
  • the apparent porosity (closed porosity) calculated from the difference between the true specific gravity and the apparent specific gravity needs to be 2% or more.
  • closed porosity When the closed porosity is less than 2%, there are relatively few closed pores as nuclei generated by vapor-grown graphite, and the reaction gas hydrogen and hydrocarbon diffuse and dissipate outside the material. Growth is inhibited.
  • a preferred closed porosity is about 2% to about 15%, more preferably about 2.5% to about 15%, and still more preferably about 2.5% to 10%.
  • Moisture is generated mainly in the temperature range of about 300 ° C. during carbonization firing of the polymer material, and water, carbon monoxide, methane, hydrogen, ammonia, etc. are generated in the temperature range of 400 ° C. or higher. Desorption and carbonization proceeds. In order to grow porous vapor-grown graphite in the subsequent hot isostatic pressing process, it is necessary to finish the carbonization and firing in a state where hydrogen remains in an appropriate amount. Specifically, it is preferable to set the carbonization firing temperature so that the amount of remaining hydrogen is 0.2 to 5% by weight.
  • the temperature for carbonization firing is usually in the range of about 400 ° C. to about 1100 ° C.
  • the carbonized and fired material adjusted to an appropriate closed porosity and residual hydrogen content is loaded into a hot isostatic pressure apparatus, and isotropically heated with an inert gas.
  • a hot isostatic pressure apparatus In order to obtain porous vapor-grown graphite, it is desirable to perform pressure heat treatment at a temperature of about 1400 ° C. or higher and a pressure of 10 MPa or higher.
  • the temperature is lower than about 1400 ° C., it is considered that vapor phase growth does not occur due to insufficient generation of hydrogen carriers and hydrocarbon carriers by excitation of hydrogen.
  • the pressure is lower than 10 MPa, diffusion and dissipation of hydrogen gas and hydrocarbon gas are accelerated, so that it is considered that the concentration and pressure of the reaction gas necessary for the vapor phase growth of graphite do not reach.
  • a preferred range of the highest temperature achieved during the hot isostatic pressing (HIP) treatment is in the range of about 1400 ° C. to about 2200 ° C., more preferably in the range of about 1500 ° C. to about 2100 ° C. .
  • the maximum ultimate pressure during the HIP treatment is about 10 MPa or more, preferably about 50 MPa or more, more preferably about 100 MPa or more, and further preferably about 180 MPa or more.
  • the upper limit value of the maximum ultimate pressure is not particularly limited, but when an HIP device is used, the upper limit value is usually determined from the performance of the device. Such an upper limit is obvious to those skilled in the art, and is usually about 200 MPa, especially about 300 MPa in the case of a high-performance apparatus.
  • a preferable pressure range can be appropriately selected from the above.
  • the isotropic pressure heat treatment it is more efficient to carry out the treatment in a pressure-preceding treatment pattern in which the pressure is kept at a pressure of 50 MPa or more and is heated to a predetermined maximum temperature by the prior carbonization firing temperature of the material to be treated.
  • vapor-grown graphite can be produced.
  • the maximum ultimate pressure at the time of HIP processing is lower than 50 MPa, the material to be treated (polymer material) is held at the maximum ultimate pressure before the carbonization firing temperature in advance, and subsequently heated to a predetermined maximum ultimate temperature. do it.
  • the carbon material of the present invention is useful because it is porous, and in particular, the total porosity is preferably 40% or more, more preferably 60% or more, and even more preferably 70% or more.
  • the carbon material of the present invention is useful because it has high graphite crystallinity, and in particular, the R value (ID / IG (I1360 / I1580)) obtained by Leraman spectroscopy measurement is less than 0.2. .
  • the amount of hydrogen is measured by an inert gas melting heat transfer method.
  • the inert gas melting heat transfer method is a method in which a sample is heated by high-frequency heating, the generated hydrogen gas is conveyed by an inert gas, and quantified by a thermal conductivity detector.
  • the measuring device used was Horiba EMGA621.
  • the closed porosity (apparent porosity) is calculated by (true density ⁇ apparent density) ⁇ true density ⁇ 100 (%) and is an index for indicating the ratio of the closed pores present in the sample to the sample volume.
  • the total porosity is calculated by (true density ⁇ bulk density) ⁇ true density ⁇ 100 (%). All pores contained in the sample, that is, closed pores that are closed spaces inside the sample and the surface of the sample It is a parameter
  • the true density is a density (mass per unit volume) measured in a state in which it is pulverized into fine powder in order to minimize the influence of voids (including open pores and closed pores) contained in the sample.
  • the volume measured by the liquid phase substitution pycnometer method was obtained by dividing the volume measured by the liquid phase substitution pycnometer method using the powder sample that passed through the 74 ⁇ m sieve.
  • Micronization is an operation for removing closed pores such as bubbles contained in the original sample.
  • a powder sample is placed in a measurement cell together with a dispersion medium such as butanol, and deaeration is performed to allow liquid to enter the voids in the sample. It is a method to seek.
  • a volume was measured using a density meter AUTO TRUE DENSER MAT-500 manufactured by SEISHIN ENTERPRISE.
  • the value obtained by dividing the sample weight by the volume thus obtained is defined as the true density.
  • the apparent density is a volume obtained by removing the volume of open pores without removing the volume of closed pores contained in the sample, and is a value obtained by dividing the weight of the sample.
  • the bulk density is a value calculated by dividing the sample weight by the volume calculated from the outer shape of the sample. Since the bulk density uses the volume calculated from the outer shape of the sample, it includes not only the volume of the sample itself but also the volume of open pores (generally pores) in addition to the volume of the sample itself. On the other hand, since the volume used for calculating the apparent density is a volume that includes closed pores but has removed open pores, the apparent density is usually higher than the bulk density.
  • the bulk density is synonymous with bulk specific gravity, the true density is synonymous with true specific gravity, and the apparent density is synonymous with apparent specific gravity.
  • the R value in the laser Raman spectroscopic measurement is 1360 cm ⁇ -1> indicating a turbulent layer structure with respect to the intensity of a peak in the vicinity of 1580 cm ⁇ -1> indicating the laminated structure of the carbon hexagonal network surface (represented as IG or I1580).
  • This is the ratio of the intensity of the nearby peaks (denoted as ID or I1360), that is, the value represented by ID / IG (I1360 / I1580).
  • a phenol formaldehyde resin was molded into a shape having an outer diameter of 100 mm and a thickness of 5 mm by hot pressing.
  • the molded resin molded body was carbonized and fired to a temperature of 950 ° C. in a nitrogen gas atmosphere.
  • the carbonized and calcined sample was heated at 110 ° C. for 2 hours, and the residual hydrogen amount was measured by an inert gas melting thermal conductivity method. As a result, 0.8% by weight of hydrogen remained.
  • the apparent porosity (closed porosity) calculated from the apparent density measured by the liquid phase substitution method and the true specific gravity measured by the liquid phase substitution method after pulverization of the sample was 7%. In the carbonization firing, the temperature range from room temperature to 200 ° C.
  • the temperature range is 20 ° C./hour, and the temperature range from 200 ° C. to 500 ° C. is 5 ° C./hour, 500 ° C. to 700 ° C.
  • the temperature range was 8 ° C./hour, and the temperature range from 700 ° C. to the highest temperature was 10 ° C./hour.
  • Example 1 The sample produced in Example 1 was filled in a hot isostatic pressure apparatus, and wasotropically heated under a maximum pressure of 1200 ° C. and a maximum pressure of 150 MPa using argon gas. The treated material was broken and the cross section was observed, but no vapor-grown graphite was produced.
  • Example 1 The sample produced in Example 1 was filled in a hot isostatic pressure apparatus, and wasotropically heated under an isotropic pressure at a maximum ultimate temperature of 1500 ° C. and a maximum ultimate pressure of 150 MPa using argon gas. When the treated material was broken and the cross-section was observed, a small amount of vapor-grown graphite was produced. The yield of vapor-grown graphite (volume ratio of vapor-grown graphite in the material) was 3%.
  • Example 1 The sample produced in Example 1 was filled in a hot isostatic pressure apparatus, and wasotropically heated with an argon gas at a maximum temperature of 2000 ° C. and a maximum pressure of 150 MPa. When the treated material was broken, a large amount of vapor-grown graphite was formed inside the material. The yield of vapor-grown graphite (volume ratio of vapor-grown graphite in the material) was 70%. Moreover, the bulk density of the obtained vapor-grown graphite was 0.3, the true density was 2.1, and the total porosity calculated from the difference between the bulk density and the true density was 86%.
  • a phenol formaldehyde resin was molded into a shape having an outer diameter of 100 mm and a thickness of 5 mm by hot pressing.
  • the molded resin molded body was carbonized and fired to a temperature of 1100 ° C. in a nitrogen gas atmosphere.
  • the carbonized and calcined sample was heated at 110 ° C. for 2 hours, and the residual hydrogen amount was measured by an inert gas melting thermal conductivity method. As a result, 0.2% by weight of hydrogen remained.
  • the apparent porosity (closed porosity) calculated from the apparent density measured by the liquid phase substitution method and the true specific gravity measured by the liquid phase substitution method after pulverization of the sample was 4%.
  • the temperature range from room temperature to 200 ° C.
  • the temperature range is 20 ° C./hour, and the temperature range from 200 ° C. to 500 ° C. is 5 ° C./hour, 500 ° C. to 700 ° C.
  • the temperature range was 8 ° C./hour, and the temperature range from 700 ° C. to the highest temperature was 10 ° C./hour.
  • Example 5 The sample produced in Example 5 was filled in a hot isostatic press, and wasotropically heated with an argon gas at a maximum temperature of 2000 ° C. and a maximum pressure of 190 MPa. When the treated material was broken, vapor-grown graphite was formed inside the material. The yield of vapor-grown graphite (volume ratio of vapor-grown graphite in the material) was 50%. Further, the vapor-grown graphite obtained had a bulk density of 0.7, a true density of 2.1, and a total porosity calculated from a difference between the bulk density and the true density of 67%.
  • a phenol formaldehyde resin was molded into a shape having an outer diameter of 100 mm and a thickness of 5 mm by hot pressing.
  • the molded resin body after molding was carbonized and fired to a temperature of 1200 ° C. in a nitrogen gas atmosphere.
  • the carbonized and calcined sample was heated at 110 ° C. for 2 hours, and the residual hydrogen amount was measured by an inert gas melting thermal conductivity method. As a result, 0.05% by weight of hydrogen remained.
  • the apparent porosity (closed porosity) calculated from the apparent density measured by the liquid phase substitution method and the true specific gravity measured by the liquid phase substitution method after pulverization of the sample was 2%.
  • the temperature range from room temperature to 200 ° C.
  • the temperature range is 20 ° C./hour, and the temperature range from 200 ° C. to 500 ° C. is 5 ° C./hour, 500 ° C. to 700 ° C.
  • the temperature range was 8 ° C./hour, and the temperature range from 700 ° C. to the highest temperature was 10 ° C./hour.
  • Example 7 The sample produced in Example 7 was filled in a hot isostatic pressure apparatus, and wasotropically heated under an isotropic pressure at a maximum ultimate temperature of 2000 ° C. and a maximum ultimate pressure of 190 MPa using argon gas. When the treated material was broken, no vapor-grown graphite was produced inside the material.
  • a phenol formaldehyde resin was molded into a shape having an outer diameter of 100 mm and a thickness of 5 mm by hot pressing.
  • the resin molded body after molding was carbonized and fired to a temperature of 450 ° C. in a nitrogen gas atmosphere.
  • the carbonized and calcined sample was heated at 110 ° C. for 2 hours, and the amount of residual hydrogen was measured by an inert gas melting thermal conductivity method. As a result, 5% by weight of hydrogen remained.
  • the apparent porosity (closed porosity) calculated from the apparent density measured by the liquid phase substitution method and the true specific gravity measured by the liquid phase substitution method after pulverization of the sample was 3%.
  • the carbonization firing was performed at a temperature increase rate of 20 ° C./hour in the temperature range from room temperature to 200 ° C., and at a temperature increase rate of 5 ° C./hour in the temperature range from 200 ° C. to the highest temperature.
  • Example 9 The sample produced in Example 9 was filled in a hot isostatic pressure apparatus, and wasotropically heated with an argon gas at a maximum temperature of 2000 ° C. and a maximum pressure of 190 MPa. The treated material burst into pieces and a large amount of vapor-grown graphite was generated around the material. The yield of vapor-grown graphite (volume ratio of vapor-grown graphite in the material) was 60%.
  • Example 1 and Example 5 were each filled in a hot isostatic pressure press, and using argon gas, isotropic pressure heating with a maximum ultimate temperature of 2000 ° C. and a maximum ultimate pressure of 10 MPa. Processed. When the treated material was broken and the cross-section was observed, a small amount of vapor-grown graphite was produced. The yield of vapor-grown graphite (volume ratio of vapor-grown graphite in the material) was 10% in all cases.
  • Example 1 and Example 5 were each filled into a hot isostatic pressure press, and using argon gas, isotropic pressure heating with a maximum ultimate temperature of 2000 ° C. and a maximum ultimate pressure of 1 MPa. Processed. When the treated material was broken and the cross-section was observed, no vapor-grown graphite was produced in any case.
  • Example 4 The sample prepared in Example 4 was immersed in a mixed aqueous solution of sulfuric acid and nitric acid to prepare a first stage graphite-sulfuric acid intercalation compound.
  • the obtained graphite intercalation compound was washed with water and then poured into a heating crucible heated to 600 ° C. for rapid heating. By rapid heating, the sample expanded about twice the volume, and a graphite material having a bulk density of 0.15 was obtained.
  • Example 4 The sample prepared in Example 4 was immersed in a mixed aqueous solution of sulfuric acid and nitric acid to prepare a first stage graphite-sulfuric acid intercalation compound.
  • the obtained intercalation compound was washed with water, and then poured into a heating crucible heated to 900 ° C. for rapid heating.
  • the graphite intercalation compound was crushed by rapid heating, and graphene-like graphite flakes having a thickness of 0.001 to 0.01 microns were obtained.
  • Example 4 The sample produced in Example 4 was cooled with liquid nitrogen and then pulverized with a metal hammer. The porous structure was destroyed by pulverization, and graphene-like graphite flakes having a thickness of 0.01 to 0.1 microns were obtained.
  • Example 1 The sample produced in Example 1 was filled in a hot isostatic pressure apparatus, and wasotropically pressurized and heat-treated at a maximum ultimate temperature of 2500 ° C. and a maximum ultimate pressure of 150 MPa using argon gas. When the material after the treatment was broken, a large amount of graphite was generated inside the material, but it was not porous and the orientation of the graphite crystal edge was not observed on the surface.
  • the yield of vapor-grown graphite (volume ratio of vapor-grown graphite in the material) was 80%.
  • the vapor-grown graphite obtained had a bulk density of 1.90, a true density of 1.96, and a total porosity calculated from the difference between the bulk density and the true density of 3%. SEM photographs of the surface of the obtained graphite are shown in FIGS.
  • FIG. 1 An example of a conventional carbon material, graphite material, and porous carbon material of the present invention is shown in FIG.
  • Natural graphite, highly oriented graphite, HOPG, quiche graphite, etc. have a high anisotropy because of their high graphite crystallinity, and as shown in the figure, the end of the carbon hexagonal network surface is only at the end of the particle or structure. Concentrated, the surface of the carbon hexagonal network is dominant on the surface. This is due to the fact that graphitization (crystallization) proceeds in the pressurizing direction and the carbon hexagonal network surface is laminated.
  • the carbon material made of porous vapor-grown graphite obtained in the present invention is a carbon material having a novel structure different from conventional carbon materials and graphite materials as shown in FIG.
  • a graphite intercalation compound using this porous graphite structure as a host material and subsequently heating it rapidly or destroying the porous graphite structure, a very thin graphene-like graphite flake is obtained as shown in FIG. Can do.
  • Table 1 The processing conditions and product status in Examples 1 to 12 and 16 of the present invention are summarized in Table 1.
  • the carbon material according to the present invention is a porous material having excellent graphite crystallinity, the end of the carbon hexagonal network surface being located on the outer surface, such as a lithium ion battery or a capacitor using an intercalation reaction with graphite. It can be suitably used for electrode materials, platinum-supported electrodes for fuel cells, various primary batteries, electrodes for secondary batteries, and the like. In addition, according to the present invention, it is possible to manufacture a large amount of the above-described novel materials at a low cost.
  • graphene-like graphite flakes can be produced by expanding and crushing the obtained porous carbon material, and electronic devices that utilize the high carrier mobility of the carbon hexagonal mesh surface (high electrical conductivity, high heat Application to conductive films, touch panels using the films, electrodes for flat displays, electrode sheets for solar cells, etc.) is realized.

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Abstract

L'invention vise à produire une matière poreuse à base de carbone, présentant un espacement approprié, un graphite à haute cristallinité et une bonne mobilité de support. L'invention concerne une matière poreuse à base de carbone dans laquelle le bord des plans hexagonaux de carbone est positionné sur la surface extérieure des particules et des structures; et du graphite floconneux de type graphène. L'invention concerne une matière à base de carbone présentant un rapport de pores fermés présents à l'intérieur de la matière et une teneur en hydrogène résiduel définis à des niveaux appropriés, qui est soumise à une compression isostatique à chaud, ce qui provoque une réaction de croissance en phase vapeur dans le graphite, les pores fermés servant de noyaux, et la réaction étant provoquée par le carbone et les hydrocarbures générés depuis l'intérieur de la matière à base de carbone. Ceci permet de produire en masse et à faible coût la matière poreuse à base de carbone selon l'invention. Des flocons de graphite de type graphène sont produits par soumission de la matière poreuse à base de graphite ainsi obtenue à un impact physique, ou par génération d'un composé s'intercalant au graphite avec la matière poreuse à base de carbone en tant qu'hôte, puis par soumission de ce composé à un chauffage instantané.
PCT/JP2010/057725 2009-05-06 2010-05-01 Matière à base de carbone et son procédé de fabrication WO2010128650A2 (fr)

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EP10772169.8A EP2431326B1 (fr) 2009-05-06 2010-05-01 Procede de fabrication d'un materiau a base de carbone
US13/266,295 US8883112B2 (en) 2009-05-06 2010-05-01 Carbon material and method for producing same
ES10772169.8T ES2606284T3 (es) 2009-05-06 2010-05-01 Método de fabricación de un material de carbono
KR1020117026928A KR101446638B1 (ko) 2009-05-06 2010-05-01 탄소 재료 및 그 제조 방법
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CN109850886A (zh) * 2019-01-18 2019-06-07 华南理工大学 一种多孔状石墨材料及其制备方法与应用
CN112816392A (zh) * 2021-03-11 2021-05-18 厦门厦钨新能源材料股份有限公司 晶态物质的闭孔孔隙率的分析测试方法

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CN104401984A (zh) * 2014-11-20 2015-03-11 东南大学 毫米尺度的石墨烯球及其大规模制备方法
CN104752703A (zh) * 2015-04-01 2015-07-01 广东烛光新能源科技有限公司 一种多孔类石墨烯及其制备方法
CN109850886A (zh) * 2019-01-18 2019-06-07 华南理工大学 一种多孔状石墨材料及其制备方法与应用
CN109850886B (zh) * 2019-01-18 2022-07-26 华南理工大学 一种多孔状石墨材料及其制备方法与应用
CN112816392A (zh) * 2021-03-11 2021-05-18 厦门厦钨新能源材料股份有限公司 晶态物质的闭孔孔隙率的分析测试方法

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